WO2002055602A1

WO2002055602A1 - Dispersion composition and ink-jet printer ink comprising the same

Info

Publication number: WO2002055602A1
Application number: PCT/JP2002/000155
Authority: WO
Inventors: Nagayuki Takao; Sachie Kawazu; Kazuki Sakai
Original assignee: Hitachi Maxell, Ltd.
Priority date: 2001-01-11
Filing date: 2002-01-11
Publication date: 2002-07-18
Also published as: US20040116552A1; US7029110B2; DE60216276T2; EP1394207A4; EP1394207A1; DE60216276D1; EP1394207B1; JP2002212447A

Abstract

A dispersion composition which comprises a colorant such as a pigment and an acrylic polymer having a furan structure; and an ink-jet printer ink characterized by comprising the dispersion composition. The dispersion composition can have satisfactory colorant dispersion stability regardless of the kind of the colorant and enables inks to be designed so as to have the same composition. The ink-jet printer ink is excellent in storage stability and printing stability.

Description

Specification

Dispersion compositions and inks for ink jet printers using the same '' Technical Field

The present invention relates to a dispersion composition and an ink for an ink jet printer using the same, and more particularly to a technical field in which a pigment or dye insoluble in a solvent is dispersed and used, for example, a paint, a printing ink, The present invention relates to a dispersion composition that can be used in the field of ink for a toner-ink jet printer, and an ink for an ink jet printer using the same. The present invention also relates to a dispersion composition which can be used in the field of a coloring material containing a coloring agent in a polymer compound by drying, such as a dry toner, a powder coating, and a plastic.

Conventional technology

Conventionally, in the field of dispersing and using pigments and dyes that are insoluble in a solvent, various methods have been used to reduce the size of the dispersed particles and to improve the storage stability. For example, UK Patent Publication No. 20000183 describes the use of certain polyesteramines as pigment dispersants in paints and inks. Japanese Patent Application Laid-Open No. Hei 9-87570 discloses a nitrogen-containing water-soluble acryl obtained by copolymerizing an α, β-ethylenically unsaturated carboxylic acid and an α, / 3-ethylenically unsaturated nitrogen-containing monomer. An aqueous pigment dispersion using a resin is described. Japanese Patent Application Laid-Open No. 2000-218486 describes a water-based ink composition for inkjet using a general acrylic acid copolymer as a dispersant. Japanese Patent Application Laid-Open No. 11-246,1818 discloses a water-based ink composition for ink jet using a block polymer. A water-based ink composition for ink jet using a polymer is described. Japanese Patent Application Laid-Open No. 11-08-633 describes an ink jet ink using colored resin particles (microencapsulated) whose face is coated with a resin having a carboxyl group. '

However, in general dispersion stabilizers and dispersion compositions using the above-mentioned pigment dispersants, the types of pigments are limited, and full-color inks such as those used for ink jet printers are required. In other fields, cyan, magenta and yellow for full color It has been developed by applying various dispersants to the four color pigments of low and black. Therefore, it was difficult to design all four colors with the same composition in ink design, and one color had to be designed for each color, which required time and effort. In addition, few ink jet inks satisfy discharge stability.

On the other hand, when block polymer graft polymer and microencapsulated pigment are used, even if it is possible to design the ink to have the same composition, it is common for polymer synthesis and microencapsulation. Compared to the synthesis of a novel copolymer, it has various disadvantages in that it costs more and more energy to obtain a dispersion composition because it goes through various manufacturing steps. '

Disclosure of the invention

Therefore, an object of the present invention is to provide a dispersion composition that satisfies the dispersion stability of a colorant regardless of the type of the colorant, and makes it possible to design ink and ink to have the same composition. In other words, it is to reduce the labor, time, cost, energy, and the like for producing ink and paint.

Another object of the present invention is to provide a colorant dispersion composition which, when used in an inkjet ink, can give the ink excellent storage stability and printing stability.

The present inventors have found that the above object can be achieved by including an acryl-based polymer compound having a furan structure in a dispersion composition containing a colorant and a polymer compound.

According to the study of the present inventors, when an acrylic polymer compound having a furan structure is used as a dispersant for a coloring agent, oxygen atoms in the furan structure are adsorbed to a highly polar portion of the coloring agent, resulting in granular particles. It has been discovered that it is possible to increase the steric repulsion between substances, prevent sedimentation of particulate matter, and enhance the dispersion stability. Thus, for example, in an aqueous dispersion composition, not only the interaction between the resin coloring agents but also the hydrophobic interaction causes an electric action between the molecules, and the coloring from hydrophobic to hydrophilic having different polarities. With regard to the ink composition, it became possible to obtain a dispersion composition with one kind of dispersant, and it became possible to design inks with the same composition. The acrylic polymer compound having a furan structure is preferably a polymer having a graft structure, a block structure, or a random structure, and is particularly preferably a polymer having a random structure because it can be synthesized without requiring complicated operations. Masure,

BEST MODE FOR CARRYING OUT THE INVENTION

The composition of the dispersion composition of the present invention is not particularly limited as long as it contains at least a coloring agent and an acrylic polymer having a furan structure.

The above-mentioned antaryl polymer compound having a furan structure must have a furan structure which is a 5-membered ring structure containing one oxygen atom.

Examples of the furan structure include frill, furfural, pyromucoic acid, furfuryl, cumarone, coumaran, phthalide, fulgide and the like. Of these, furfuryl is preferred because of its high resorptivity and adsorptivity.

Further, the acrylic polymer compound having a furan structure is an acryl-based polymer obtained by copolymerizing at least a monomer having a furan structure and one of other monomers having a solubility parameter of 9.5 or less. Molecular compounds are preferred. Other monomers are used to interact with the hydrophobic part of the colorant, which is particularly hydrophobic, and to improve the dispersion stability of the colorant.

Examples of the monomer having a furan structure include tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate, and the like.

Monomers with a solubility parameter of 9.5 or less include methacrylic acid Λ ^, ethyl acrylate, isopropyl olenoate, acrylic acid- η-propyl, acrylic acid η-butyl, and acrylic acid-t -Butyl, benzyl atalinoleate, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, tridecyl methacrylate, benzyl methacrylate 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, otatyl acrylate, octyl methacrylate, lauryl acrylate, lauryl methacrylate, cetyl acrylate, cetyl methacrylate, stearyl acrylate, stearyl methacryl (Meth) acrylic esters such as latet, behenyl acrylate, behenyl methacrylate, etc .; styrene, α-methinolestyrene, o-methinolestyrene, m-methinole Styrene, p-methylstyrene, styrene-based monomers such as p-tert-butylstyrene; vinyl acetate; alpha-olefins such as ethylene. Among them, styrene-based monomers and (meth) acrylate-based monomers having an alkyl group having more than 4 carbon atoms and having an alkyl group larger than 4 are particularly preferable because they improve the affinity with the colorant.

Akuriru polymer compound having a furan structure, a monomer having a furan structure, preferably 3-5 0 weight ⁰ /. Range, more preferably in the range of 5-4 0 weight ^_0/0. If the proportion of the monomer having a furan structure is less than 3% by weight, the interaction between the polymer compound and the high-polarity colorant is weak, and if it is more than 50% by weight, the polarity of the dispersant is high. The interaction with the highly water-based colorant is weakened, and the dispersion stability of the colorant cannot be improved.

The acid value of the acryloline polymer having a furan structure is preferably in the range of 30 to 40 Omg KOH / g, more preferably in the range of 50 to 30 Omg KOHZg. In the aqueous dispersion composition, if the acid value is less than 3 O mg KOHZ g, the solubility of the polymer compound in water becomes weak, and the colorant becomes difficult to disperse, and the acid value is more than 400 mg KOH / g. And the interaction with the colorant is weakened, resulting in poor dispersion stability.

Preferred examples of the monomer giving an acid value include acrylic acid, methacrylic acid, oxalic acid, etaatalylic acid, propyl acrylic acid, isopropyl acrylic acid, itaconic acid, fumaric acid, and acryloyl shexyl phthalate. Monomers having a carboxyl group such as acryloxysuccinate; monomers having a sulfonic acid group such as ethyl 2-sulfonate acrylate, ethyl 2-sulfonate, and butylacrylamide sulfonate; methacrylic acid 2 —Monomer having a phosphonic acid group, such as ethyl phosphonate, 2-ethyl acrylate, etc., among which monomers having a carboxyl group are more preferable, and allylic acid and methacrylic acid are particularly preferable. Les ,.

The ataryl polymer compound having a furan structure preferably has a weight average molecular weight in the range of 300 to 500, more preferably in the range of 400 to 400. If the weight average molecular weight is less than 300, the dispersion stability becomes poor, and If it exceeds 50,000, the viscosity of the ink becomes high, making printing and painting difficult.

Examples of monomers usable for the acrylic polymer compound having a furan structure include, in addition to the above monomers, for example, itaconic acid esters such as benzyl itaconate; maleic esters such as dimethyl maleate; dimethyl fumarate; Fumaric acid esters such as: acrylonitrile, methacrylic acid, rilonitrile, vinyl acetate; 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, glycerol monomethacrylate, Hydroxyl-containing monomers such as polyethylene glycol monomethacrylate, propylene glycol / monomethacrylate, polyethylene glycol monoacrylate, propylene glycol monoacrylate; glycidyl acrylate Glycidyl group-containing monomers such as glycidyl methacrylate; methoxy group-containing monomers such as methoxypolyethylene glycol methacrylate, methoxypolyethylene glycol methacrylate, acrylamide, methacrylamide, atalylic amide, and amide amino acrylate Monomers having a primary amino group such as aminopropyl linoleate, methacrylic acid amide, aminoethyl methacrylate, aminopropyl methacrylate, methylaminoethyl acrylate, methylaminopropyl acrylate, and ataryl acid Thilaminoethyl, ethylaminolate acrylate, mouth pill, methylaminoethyl methacrylate, methylaminopropyl methalolinate, ethylaminoethyl methacrylate, ethylaminopropyl methacrylate, 2 Monomer having a secondary amino group such as vinyl pyridine, 4-vinyl pyridine, etc., dimethylaminoethyl acrylate, getylaminoethyl acrylate, dimethylaminopropyl acrylate, getylamino acrylate Monomers having a tertiary amino group, such as dimethylaminoethyl methacrylate, methacrylate !, dimethylaminoethyl ethyl methacrylate, dimethylaminopropyl methacrylate, and dimethylaminoethyl methyl acrylate acrylate Dimethylaminoethyl methyl methacrylate methacrylate, dimethylaminoethyl benzyl acrylate salt, dimethylaminoethyl benzyl methacrylate Monomers having a quaternary amino group such as sulfide salts; amino-containing monomers such as; and silicone monomers are preferred.

When synthesizing the acrylic polymer compound having a furan structure, a known polymerization initiator can be used. Preferred examples of the polymerization initiator include tert-butyl / levoxybenzoate, ze-ptinoleperoxide, cumene hydroxide, acetyl peroxide, benzoyl peroxide, lauroyl peroxide, and the like. And perazo compounds such as azobisisobutyltylonitrile, azobis-1,2,4-dimethylvaleronitrile, and azobiscyclohexyl benzonitrile.

Further, the acrylic polymer compound having a furan structure can be synthesized in a solvent. Preferred examples of the solvent include: aliphatic hydrocarbon solvents such as hexane and mineral spirit; aromatic hydrocarbon solvents such as benzene, toluene and xylene; ester solvents such as butyl acetate; methanol and butanol. Alcohol solvents such as toluene, isopropyl alcohol, and ethanol; ketone solvents such as methyl ethyl ketone and isobutyl methyl ketone; non-solvents such as dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, and pyridine. Protic polar '14 solvents, water and the like. Among them, a water-soluble solvent such as isopropyl alcohol-methylethyl ketone is more preferable. In addition, two or more of these solvents may be used in combination.

As the reaction method, known general methods such as bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, and redox polymerization are preferable, and among them, tooth polymerization is more preferable because the reaction method is simple.

The polymerization reaction conditions vary depending on the type of polymerization initiator, solvent, etc., but the reaction temperature is 180 ° C. or lower, preferably 30 ° C. to 150 ° C., and the reaction time is 30 minutes to 40 hours. It is preferably 2 hours to 30 hours.

As the colorant contained in the composition of the present invention, inorganic pigments, organic pigments, disperse dyes and the like are preferable.

Inorganic pigments include, for example, carbon black, titanium oxide, zinc oxide, zinc oxide, tripon, iron oxide, aluminum oxide, silicon dioxide, kaolinite, Morillonite, Tanolek, Barium sulfate, Calcium carbonate, Silica, Alumina, Forced mullet, Bengal, Molybdenum red, Coupe mupermillion, Molybdate orange, Graphite, Chrome yellow, Cadmium yellow, Yellow iron oxide, Titan yellow, Pyrochrome Cobalt green, titanium cobalt green, cobalt chrome green, ultramarine blue, ultramarine blue, navy blue, cobalt punoray, cerulean bunore, manganese violet, cobalt violet, mica and the like are preferable.

Examples of organic pigments include azo, azomethine, polyazo, phthalocyanine, quinatalidone, anthraquinone, indigo, thioindigo, quinophthalone, benzimidazolone, isoindoline, and isoindolin. Linone pigments and the like are preferred.

As the disperse dye, for example, azo type, anthraquinone type, indigo type, phthalocyanine type, carbonyl type, quinonimine type, methine type, quinoline type, nitro type and the like are preferable.

In the dispersion composition of the present invention, the amount of the acrylic polymer compound having a furan structure is preferably 2 to 100 parts by weight, more preferably 100 to 100 parts by weight of the coloring agent. Is in the range of 5 to 500 parts by weight. If the amount of the polymer compound is less than 2 parts by weight, the dispersion stability is poor, and if it exceeds 100 parts by weight, the content of the colorant in the dispersion composition is reduced, for example, paints, inks, toners, etc. It is difficult to obtain a sufficient concentration of the particulate matter for use in wastewater. The amount of the colorant is preferably in the range of 1 to 50% by weight, more preferably 5 to 40% by weight, in 100 parts by weight of the dispersion composition. Colorant amount 1 weight ⁰ /. If it is smaller, the color density will be too low when used in inks and paints, making it impractical. If it is more than 50% by weight, the viscosity will be too high and handling will be difficult.

Solvents that can be used in the dispersion composition of the present invention include aliphatic hydrocarbon solvents such as hexane and mineral spirit; silicone oils such as dialkylpolysiloxane and cyclic polydialkylsiloxane; and olive oil. Vegetable oils such as safflower oil, sunflower oil, soybean oil and linseed oil; benzene, toluene, kishi Aromatic hydrocarbon solvents such as lene; Ester solvents such as butyl acetate; Alcohol solvents such as methanol, ethanol, isopropyl alcohol, and butanol; Methino ethynole ketone, Isoptin ole methyl ketone Ketone solvents; aprotic polar solvents such as dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone, pyridine and the like; water; and water, and water-soluble solvents soluble in water are more preferable. These solvents can be used alone or as a mixture of two or more.

The dispersion composition of the present invention can be produced by a conventional method using a commonly used dispersing machine. As the dispersing machine, a container driving medium mill such as a mouth mill, a ball mill, a centrifugal mill, and a planetary pole mill, and a high-speed rotating mill such as a sand mill are available.

As a specific method for producing a dispersion composition, the acryl-based polymer compound having a furan structure is neutralized with a neutralizing agent, dissolved in water, and then a colorant is added and uniformly mixed. . Next, if necessary, an antifoaming agent or a water-soluble organic solvent is added, and the mixture is dispersed using the above-mentioned dispersing machine until a desired particle size is obtained. Further, the dispersion composition may be subjected to heat treatment at 40 ° C. to 100 ° C. in order to stabilize the dispersion.

As a dispersion medium used in the dispersing machine, glass beads, steel beads, ceramic beads and the like are used, and among them, ceramic beads having a particle size of 0.01 to 1.0 mm are preferably used.

The dispersion conditions in this case are not particularly limited. However, it is preferable that the dispersion be performed at an acceleration of 5 to 5 G in a planetary ball mill, at a filling ratio of ceramic beads of 50 to 90% in a sand mill, and at a peripheral speed of 5 to 20 mZs. '' Examples of the above neutralizing agents include monovalent alkali metal ions such as lithium hydroxide, sodium hydroxide, and hydroxylating lime, ammonia, triethi / reamine, triethano monooleamine, jetanoreamine, and ethanolamine. And organic amines such as dimethinoleaminoethanol. In particular, a non-volatile neutralizing agent is preferable when used in an ink jet ink, because it can prevent clogging at the head. The use of the dispersion composition of the present invention is not particularly limited, but includes the fields of paints, printing inks, inks for toner and ink jet printers, etc., and is particularly preferably used as an ink for ink jet printers.

The composition of the ink for an ink jet printer using the dispersion composition of the present invention is not particularly limited as long as the composition contains the above dispersion composition. This ink contains various additives conventionally used in inks for inkjet printers, such as water-soluble organic solvents,: H adjusters, surfactants, anti-clogging agents for print heads, and defoamers for inks. Also, a bactericide, an antifungal agent, a water-resistance imparting agent for printing, a charge control agent, and the like can be added.

The proportion of the dispersion composition used in the ink for an ink jet printer of the present invention is preferably such that the proportion of the colorant in the ink 100% double haze is in the range of 1 to 10% by weight. If the proportion of the coloring agent is less than 1% by weight, no image density can be obtained, and if it is more than 10% by weight, the viscosity becomes too high and printing becomes impossible. The ink for an ink jet printer of the present invention contains at least one water-soluble organic solvent selected from the group consisting of water-soluble polyhydric alcohols to suppress drying, and after drying, the colorant is redispersed in the solvent. It is preferable that redispersibility is achieved 1 ヽ. The amount of the water-soluble organic solvent to be added is preferably for Inku 1 0 0 wt%, 4-3 0 weight / _0, more preferably in the range of 4-2 0% by weight. If the Blend amount of water 'I ¹ raw organic solvent 4 wt% or more, improved results of anti-clogging properties of the head to the print becomes sufficient. On the other hand, if the amount of the water-soluble organic solvent is less than 30% by weight, the organic property of the solution is lowered, thereby preventing defects such as disturbing the dispersibility of the colorant. Examples of the water-soluble organic solvent include ethylene glycol, diethylene glycol ', and glycerin. Further, other organic solvents and various additives can be used in combination. For example, triethylene glycol, tripropylene glycol, dimethyl sulfoxide, diacetone alcohol, glycerin monoaryl ether, propylene glycol, polyethylene glycol, thiodiglycol, N-methyl-2-pyrrolidone, 2-pyrrolidone, γ-butyrolataton, 1,3-Dimethyl-1-2-imidazolidinone, snoreforan, trimethylolpropane, neopentyl-gluene, ethylene glycol monomethyl ether, ethylene glycol Ricohone monoethynoleate, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl allyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, triethylene glycol monomethyl ether, triethylene glycol Ethylene glycol monoethyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethynooleate, 1, dihydroxoxetinourea, urea, acetoninoletone, pentaerythritol Xylene glycolonele, ethylene glycol monopropynoleatenole, ethylene glycol monobutyleeneolene, ethylene glycol monoisobutylinoleateneolete, ethylene glycoloneleonele Eninolete, Diethyleneglyconele Retinore, Tenethylenglyconele Monopinoleatenole, Detyleneglyconelenolemo Neusopti / Retetele, Triethyleneglyconele Monobutylatenole, Trietiglyconele Athenole, triethylene glycolone retinoate ethereone, tetraethylene glycol dimethyl ether, tetraethylene glycol methyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether , Tripropylene glycol monomethyl ester glycerin monoacetate, glycerin diacetate, glycerin triacetate Acetate, ethylene glycol monomethinoleate enorea acetate, diethylene glycol monomethyl ether acetate, cyclohexanol, 1-butanol, 2,5-hexanediol, ethanol, n-propanol, 2-propanol, 1-methoxy-2 —Propanol, furfuryl alcohol, tetrahydrofurfurinoleanolone, 1,2-butanediol, 1,4-butanediole, 1,3-butanediole, 2,4-pentanediole, 1,5 —Pentanediole, 2-Methynole-1,2,4-Pentanediole, 1,2-Cyclohexanedioleone, 1,4-Cyclohexanediol, Trimethylolethane, Trimethylolpropane, 1,2 , 4-butanetriol, 1,2,6-hexanetriol, 1,2,5-penta Triol, 3-methyl-1,5-pentanedionole, 3-hexene-1,2,5-diol, polyethylene glycol, polypropylene glycol, etc., and a mixture of two or more of these. Is also good. As the pH adjuster, at least one selected from water-soluble inorganic salts or hydroxides is used so that the pH of the prepared ink for an ink jet printer is in the range of 7 to 10. Adjust to As a result, clogging of ink nozzles can be effectively prevented. Examples of ZR-soluble inorganic salts include sodium carbonate and calcium carbonate. Examples of water-soluble inorganic hydroxides include lithium hydroxide, sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide and the like. No.

Further, it is preferable to add a resin to the ink for an inkjet printer of the present invention for the purpose of improving the water resistance, luster, and abrasion resistance of the printed matter. Examples of the type of the resin include a water-soluble resin and a dispersion-type resin having an average particle diameter of 10 to 300 nm. Examples of the chemical structure of the resin include acrylic, vinyl, polyester, and amide copolymers thereof. The amount of these added is preferably in the range of 1 to 15% by weight, more preferably in the range of 2 to 10% by weight, out of 100% by weight of the ink, in view of various properties.

Examples of the above defoaming agents include cationic activating agents such as alkyl benzene sulfonic acid type, alkyl sulphate ester type, fatty acid salt type and quaternary ammonium salt type, or amphoteric interface such as alkyl betaine and amine oxide. Examples of the activator include a nonionic surfactant, and an organic silicone-based nonionic surfactant such as a methylpolysiloxane copolymer. Examples of the fungicide and fungicide include benzoate, alkylamine salt and quaternary ammonium salt. Examples of the antifoaming agent include fatty acid esters such as sorbitan acid ester, polyoxyethylene alkyl ether, and silicone oil.

Further, it is preferable to add a surfactant to the ink of the present invention, since the printing stability is improved. In particular, by adding a surfactant, a thermal-type ink jet printer can stably generate purple when heated by a heater. The addition amount of the surfactant is preferably in the range of 0.5 to 5% by weight in view of printing stability.

In consideration of the above printing stability, the surfactant is preferably a water-soluble ionic surfactant or a nonionic surfactant having an HLB value of 12 or more. The type is not particularly limited as long as the water-soluble power or HLB value is 12 or more, and anionic surfactant, Any of a surfactant, a nonionic surfactant, and an amphoteric surfactant can be used. Of these, particularly preferred surfactants are anionic surfactants and nonionic surfactants.

Examples of the aionic surfactants include fatty acid salts such as sodium stearate soap, potassium soap oleate and semi-hardened tallow fatty acid soda soap; sodium lauryl sulfate, and triethanolamine lauryl sulfate. Alkyl sulfates such as sodium higher alcohol sulfate; alkylbenzene sulfonates such as sodium dodecylbenzenesulfonate; alkyl naphthalene sulfonates such as sodium alkyl naphthalene sulfonate; alkyl sulfosuccinates such as sodium dialkyl sulfosuccinate; Alkyl diphenyl ether disulfonates such as sodium alkyl diphenyl ether disulfonate; alkyl phosphates such as alkyl phosphoric acid rims; sodium polyoxoxylene lauryl ether sulfate sodium polyoxyalkylene; Polyoxyethylene alkyl sulfate esters such as triethanolamine sulfate; alkylaryl sulfate salts such as polyoxyethylene alkyl phenyl ether sodium sulfate; polyoxyethylene alkyl sulfate; naphthalene sulfate Acid formalin condensates and the like.

Examples of the cationic surfactants include alkylamine salts such as coconutamine acetate and stearylamine acetate, lauryltrimethylammonium chloride, stearyltrimethylammonium chloride and alkylbenzyldimethanolamine ammonium. Examples include quaternary ammonium salts such as dimethyl chloride, alkyl betaines such as lauryl betaine and stearyl betaine, and amine oxides such as lauryl dimethyl amine oxide.

Examples of nonionic surfactants having an HLB value of 12 or more include, for example, polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, and polyoxyethylene high alcohol ester. Polyoxyethylene alkyl ethers, such as polyoxyethylene octyl phenylene ether and polyoxyethylene nonoleno phenol, and polyoxyethylene alkyl ethers; polyoxyethylene derivatives, polyoxyethylene derivatives, and oxyethylene. Propylene block copolymer, sorbitan fat Polyoxyethylene sorbitan fatty acid esters such as acid esters, polyoxyethylene sorbitan monolaurate, polyoxyethylene, polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan monooleate and polyoxyethylene sorbitan trioleate; Examples include nonionic surfactants such as polyoxyethylene sorbitol fatty acid esters such as polyoxyethylene sorbite oleate, glycerin fatty acid esters, and acetylene glycol. When the ink for an ink jet printer of the present invention is used in an ink jet printer of a type that adds a charge to the ink, an electrolyte may be added in order to adjust the conductivity of the ink to a predetermined value. However, the required conductivity differs depending on the printer model, and the conductivity of the ink also differs depending on other components in the ink. Examples of electrolytes that can be used for such purposes include ammonium chloride, sodium chloride, lithium nitrate, ammonium nitrate, ammonium thiocyanate, potassium thiocyanate, sodium thiocyanate, ammonium nitrite, lithium acetate, and acetate. Inorganic salts such as potassium and ammonium acetate; triethanolamine hydrochloride; triethanolamine nitrate; and triethanolamine sulfate.

In order to manufacture the ink for an ink jet printer of the present invention, a commonly used stirrer is used, and it is not necessary to use a disperser having a particularly strong dispersing ability. The ink for an ink jet printer according to the present invention can be used in any printer without particular limitations on the type of ink jet system, as long as it is a commercially available ink jet system such as a piezo type general type or a continuous type. For example, as described in Japanese Patent Application Laid-Open No. 08-109433, U.S. Pat. No. 4,255,755, and the like, it can be used in a printer and printed. .

Example

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples.

In the following description, “parts” and “%” mean “parts by weight” and “% by weight”, respectively, unless otherwise specified. Made trial Drug Class 1 was used. The particle size of the pigment and the disperse dye used and the measurement of the dispersed particle size were measured using a laser-Doppler type Coulter particle size distribution analyzer N4PLUS. Synthesis example 1

Preparation of acryl-based polymer compound having furan structure

A solution was prepared by mixing the following components:

n-butyltyl acrylate 37. 9 parts Lauryl methacrylate 20.0 parts Tetrahydrofurfuryl methacrylate (manufactured by Kyoeisha Chemical Co., Ltd.) 20.0 parts Acrylic acid '. 22. 1 part Perhexyl O (manufactured by NOF Corporation) 8.0 parts Next, 100 parts of isopropyl alcohol was placed in a reaction vessel equipped with a nitrogen inlet tube, and the temperature was raised to the reflux temperature while sealing with nitrogen. The above solution was added dropwise over 2 hours. After completion of the addition, the mixture was reacted at reflux for 14 hours. The solution after the reaction contained a polymer compound having an acid value of 159 KOHmgZg and a weight-average molecular weight of 9,500 with a volatile content of 52.1%. This was neutralized 100% with sodium hydroxide, and then isopropyl alcohol was replaced with ion exchanged water to prepare a 50% aqueous solution. Synthesis example 2

Preparation of acryl-based polymer compound having furan structure

A solution was prepared by mixing the following components:

n-butyl atylate 42. 9 parts Styrene 20.0 parts Tetrahydrofurfuryl acrylate (manufactured by Kyoeisha Chemical) 15.0 parts Acrylic acid 22.1 parts 1 ^ ^ xino o (Peroxy manufactured by NOF Corporation) Ester) 4.0 parts Next, 100 parts of isopropyl alcohol was charged into a reaction vessel equipped with a nitrogen inlet tube, and the temperature was raised to the reflux temperature while sealing with nitrogen. The solution was added dropwise over 2 hours, and after the completion of the addition, the mixture was reacted at a reflux temperature for 14 hours. The solution after the reaction had a volatile content of 51.9%, an acid value of 15.7 KOHmgZg, and a weight-average molecular weight of 18,000. Child compounds. This was neutralized 100% with sodium hydroxide, and isopropyl alcohol was replaced with ion-exchanged water to prepare a 50% aqueous solution.

Synthesis example 3

Preparation of Ataryl Polymer Compounds Having Furan Structure

A solution was prepared by mixing the following components:

n-butylacetylate 47.0 parts lauryl methacrylate 20.0 parts tetrahydrofurfuryl methacrylate (manufactured by Kyoeisha Chemical Co., Ltd.) 20.0 parts acrylic acid .13.0 parts perhexinole resin (manufactured by NOF Corporation) 8.0 parts Next, 100 parts of isopropyl alcohol was charged into a reaction vessel equipped with a nitrogen inlet tube, and the temperature was raised to the reflux temperature while sealing with nitrogen. The solution was added dropwise over 2 hours, and after the completion of the addition, the mixture was reacted at a reflux temperature for 14 hours. The solution after the reaction contained a polymer compound having a non-volatile content of 52.3%, an acid value of 92 KOHmg7g, and a weight average molecular weight of 9,400. This, 100 ^o / ₀ and neutralized with sodium hydroxide, to replace the Isopuropi alcohol in Ion-exchanged water to prepare a 50% aqueous solution.

Synthesis example 4

Preparation of acryl-based polymer compound having furan structure

A solution was prepared by mixing the following components:

η-Butyl acrylate 28.8 parts Lauryl methacrylate 20.0 parts Tetrahydrofurfuryl methacrylate (manufactured by Kyoeisha Chemical) 20.0 parts Acrylic acid 31.2 parts Perhexyl. (Peroxy manufactured by NOF Corporation) Ester) 8.0 parts Next, 100 parts of isopropyl alcohol was charged into a reaction vessel equipped with a nitrogen inlet tube, and the temperature was raised to the reflux temperature while sealing with nitrogen. The solution was added dropwise over 2 hours, and after the completion of the addition, the mixture was reacted at a reflux temperature for 14 hours. The solution after reaction had a volatile content of 52.5%, an acid value of 22 lKOHmg / g, and a weight-average molecular weight of 5400. Child compounds. This was neutralized 100% with triethanolamine, and isopropyl alcohol was replaced with ion-exchanged water to prepare a 50% aqueous solution. Synthesis example 5

Preparation of styrene-acrylic acid resin

A water-soluble acryl polymer was synthesized by the following procedure in accordance with the examples of JP-A-2000-212486.

The ingredients were mixed and a solution was prepared:

Acrylic acid 15.7 parts Styrene 84.3 parts Perhexyl O (Peroxyester manufactured by NOF CORPORATION) 8.0 parts Next, 100 parts of methyl ethyl ketone are placed in a reaction vessel equipped with a nitrogen inlet tube. The temperature was raised to the reflux temperature while sealing with nitrogen. The solution was dropped over 2 hours, and after the completion of the dropping, the mixture was reacted at a reflux temperature for 14 f. The solution after the reaction contained a polymer compound having a nonvolatile content of 51.9%, an acid value of 118 KOHmgZg and a weight average molecular weight of 8000. This was neutralized 100% with sodium hydroxide, and methylethyl ketone was replaced with ion-exchanged water to prepare a 50% aqueous solution.

Synthesis example G

Preparation of graft polymer

A graft polymer was prepared according to the following procedure in accordance with the example of JP-A-10-87768. 3 The synthesis was much more time-consuming than the above random polymer. Preparation of macromonomer

Part 1:

Isopropanol 530 · .5 parts Acetone 77.5 parts Methacryloleic acid 70, 1 part Ethoxytriethylene glycol methacrylate 12.4 parts Part 2:

Ziaquabis (Hoguchi Njibrodilogihue-Riglioximato) Cobalt (II)

0.10135 copies 2,2'-Azobiz (2,2-methylbutylnitrile) 0.7 8 parts Acetone '2 1.5 parts Part 3'

Methacrylic acid 2 80.1 parts-Ethoxytriethylene glycol methacrylate 49.4 parts

'' Part 4

Diaquabis (holondiborodifenilaryoximat) Cobalt (II)

0.10 3 5 parts

2,2'-azobis (2,2-methylbutylnitrile) 4.5 parts Acetone 4 7.5 parts Part 5

Diaquabis (holon difluoride fendalioximato) cobaltate (Π)

0.04 1 copy

2,2'-Azobis (2,2-dimethylvaleronitrile) 2.3 parts Acetone 4 0.5 parts Part 6

Diaquabis (holon difluoride fendalioximato) cobaltate (Π)

0.06 2 parts

2,2'-azobis (2,2-dimethylvaleronitrile) 2.3 parts Acetone 40.5 parts These components were mixed part by part to prepare solutions of parts 1 to 6.

Next, the solution of Part 1 was charged into a 3 L reaction vessel equipped with a nitrogen inlet tube, heated to a reflux temperature while nitrogen sealing, and maintained at the reflux temperature for 20 minutes. The solution of Part 2 was added, and the solution of Part 3 and the solution of Part 4 were added in parallel over 4 hours and 90 minutes, respectively, while maintaining the reflux temperature (72 D). After the addition of the solution of Part 4 was completed, the solution of Part 5 was added over 75 minutes. Subsequently, the solution of Part 6 was added over 75 minutes, and after completion of the addition, the reflux temperature was maintained for an additional hour to terminate the reaction and obtain a macromonomer.

Preparation of graft polymer Part 1

Kamimojima Macronomer 114. 9 咅 2-pyrrolidone 20.0 Part 2

t-Putinole peroxypivalate 1.1 parts Acetone 10.0 parts Part 3

Benzyl acrylate 64.2 parts 2-Pyrrolidone 20.0 parts Part 4

t-Peptinolenoleoxypiparate 2.3 parts Acetone 20.0 parts Part 5

t-Peptinolenorreoxypivalate 1.1 part Acetone 0.0 part Charge the components of Part 1 into a 500 mL reaction vessel equipped with a nitrogen inlet tube, raise the temperature to the reflux temperature while sealing with nitrogen, and reflux. The temperature was maintained for 10 minutes. The component of Part 2 was added, and the components of Part 3 and Part 4 were simultaneously added over 3 hours while maintaining the reflux temperature. After the addition was completed, the reaction was continued at the reflux temperature for 1 hour, and the component of part 5 was added. Subsequently, reflux was continued at a reaction temperature of 66 for 2 hours. Further, 74.5 parts of volatile matter was distilled off, and 11.6 parts of 2-pyrrolidone was added to obtain a graft polymer.

The synthesis of this polymer is much more time-consuming than Synthetic Examples 1-4, and therefore, it takes much time and cost to make the ink as a whole.

Example 1 The following substances were dispersed in a sand mill for 1 hour using zirconia beads having a particle size of 0.3 mm to obtain a dispersion composition.

'Black pigment (made by Dedasa, trade name: Printex 75) 20.0 parts by weight

8.0 parts by weight of polymer compound of Synthesis Example 1 72.0 parts by weight of ion-exchanged water The dispersed particle size of the pigment in the dispersion composition was 87 nm.

Using this dispersion composition, a black ink for an ink jet printer having the following composition was prepared.

The above dispersion composition 22.5 parts by weight Glycerin 8.0 parts by weight Diethylene glycol 5.0 parts by weight Trimethylonolepropane 7.0 parts by weight S-120 (HLB 12.8 sorbitan surfactant): Kao Corporation )

2.0.0 parts by weight Ion-exchanged water 57.5 parts by weight Next, the above black pigment was changed to the following pigment, and the cyan dispersion composition, cyan ink, magenta dispersion composition, magenta ink, and yellow dispersion liquid were used. A yarn composition and yellow ink were prepared.

Cyan pigment: Fastoge en Blue TGR (Dainippon Ink and Chemicals Magenta Pigment: Fastoge En Sup e r Mg Enta RTS (manufactured by Dainippon Ink and Chemicals, Inc.)

Yellow pigment: Symu 1 e r Fas t Yel low 4190, (Dainippon Inky ^ Gaku Kogyo Co., Ltd.)

Table 1 shows the properties of the dispersion composition and the ink. The ink using the above dispersion composition was excellent in storage stability and, as a result of printing evaluation with Canon BJF-6000, showed extremely excellent characteristics as shown in Table 1. In addition, since these dispersion compositions were prepared using the same polymer compound, it was possible to reduce the problem of preparing an ink and to reduce energy.

Comparative Example 1

A black dispersion composition, a black ink, and a black ink were prepared in the same manner except that the styrene acryl resin of Synthesis Example 5 was used instead of the polymer compound of Synthesis Example 1 in Example 1. A liquid dispersion composition, a cyan ink, a magenta dispersion liquid composition, a magenta ink, a yellow dispersion liquid composition, and a yellow ink were prepared.

Compared to Example 1, the yellow and magenta inks using these dispersion compositions had a large particle size after long-term storage, poor storage stability, and a full-color ink with the same polymer compound as shown in Table 1. Could not be offered. In addition, as a result of printing evaluation using Canon 8-600, as shown in Table 1, the printing characteristics of magenta and yellow ink were not satisfactory.

Example 2

In the same manner except that 12 g of the polymer compound of Synthesis Example 2 was used instead of the high molecular weight compound of Synthesis Example 1 in Example 1, a black dispersion composition and a black ink, a cyan dispersion composition and A cyan ink, a magenta dispersion composition, a magenta ink, a yellow dispersion composition, and a yellow ink were prepared. The cyan, magenta, yellow, and black inks using these dispersion compositions have excellent storage stability as shown in Table 1, and have been evaluated for printing with Canon BJF-600. As shown in the figure, excellent characteristics were exhibited. In addition, since these dispersion compositions were prepared using the same high molecular compound, the labor and energy required for preparing the ink could be reduced.

• Example 3

A black dispersion composition, a black ink, and a cyan dispersion liquid were prepared in the same manner except that 12 g of the polymer compound of Synthesis Example 3 was used instead of the polymer conjugate of Synthesis Example 1 in Example 1. The composition, a cyan ink, a magenta dispersion composition, a magenta ink, a yellow dispersion composition, and a yellow ink were prepared. The cyan, magenta, yellow, and black inks using these dispersion compositions exhibited excellent storage stability as shown in Table 1, and also exhibited extremely excellent printing characteristics. In addition, since these dispersion compositions were prepared using the same polymer compound, the time and energy required for preparing the ink could be reduced.

Example 4

The following composition was dispersed in a sand mill using zirconia beads having a particle size of 0.3 mm for 2 hours to obtain a dispersion composition. ' -Black pigment (manufactured by Dedasa, trade name: Printex75) 2,0.0 parts by weight

''12 .0 parts by weight of polymer compound of Synthesis Example 4

'Ion-exchanged water. 68.0 parts by weight. The dispersed particle size of the pigment in the dispersion composition was 87 nm.

Using this dispersion composition, a plaque ink for an ink jet printer was prepared with the following composition. '

The above dispersion composition 22.5 parts by weight Glycerin 9.0 parts by weight Sodium benzoate 0.05 parts by weight Lithium nitrate 0.27 parts by weight Acetylene glycol 0.06 parts by weight Deionized water 68.12 parts by weight By changing the black pigment to the following pigment, a cyan dispersion composition and a cyan ink, a magenta dispersion composition and a magenta ink, a yellow dispersion composition and a yellow ink were produced.

, Pigment: Faststone Blue TGR (Dainippon Ink and Chemicals Magenta Pigment: Faststone Ener Su MgRenta RTS (Dainippon Ink and Chemicals)

Yellow pigment: Symu 1 er Fas t Yel ow 4192 (Dainippon Ink & Chemicals, Inc .: t¾).

Table 1 shows the properties of the dispersion composition and the ink. The ink using the above-mentioned dispersion composition was excellent in storage stability and, as a result of printing evaluation using a continuous ink-jet printer manufactured by Cytex, showed very excellent characteristics as shown in Table 1. In addition, since these dispersion compositions were prepared using the same polymer compound, the labor and energy required for preparing the ink could be reduced.

Comparative Example 2 In place of the polymer conjugate of Synthesis Example 4 in Example 4, a commercially available styrene acryl resin (Johncryl 679 L sodium hydroxide neutralized product manufactured by Johnson Polymer Co., Ltd.) Preparation of Black Dispersion Composition, Black Ink, Cyan Dispersion Composition, Cyan Ink, Magenta Dispersion Composition, Magenta Ink, Yellow Dispersion Composition, and Yellow Ink . Compared with Example 4, the yellow and magenta inks using these dispersion compositions became larger in particle size after long-term storage as shown in Table 1 below, and had poor storage stability. Full strength inks have not been available. Table 1 summarizes the characteristics of Examples 1 to 4 and Comparative Examples 1 and 2.

table 1

The particle size was measured with a laser Doppler type particle size distribution meter N 4 PLUS manufactured by Coulter, Inc. The viscosity was measured with a Toki Sangyo Women R-type viscometer (rotational speed 100 rpm). In addition, the printing stability of the printing evaluation is as follows. The thing was X. The reliability is as follows. After leaving the ink in the printer for 1 month at room temperature, printing is performed. Prints that can be printed without cleaning. X cannot be printed even after printing. The dispersion composition of the present invention can satisfy the dispersion stability of a colorant irrespective of the type of the colorant, and can be designed to have the same composition of the ink, to produce an ink or a paint. The labor, time, cost, energy, etc. were reduced. In addition, the ink jet ink of the present invention was able to provide an ink having excellent storage stability and printing stability by using the dispersion composition of the above invention.

Claims

The scope of the claims

1. A dispersion composition containing a colorant and an acryl-based polymer compound having a furan structure.

2. The dispersion composition according to claim 1, wherein the furan structure is furfuryl.

3. The dispersion composition according to claim 1, wherein the polymer compound is a copolymer of a monomer having a furan structure and at least one monomer having a solubility parameter of 9.5 or less.

4. The dispersion composition according to claim 3, wherein the polymer compound contains a monomer having a furan structure in an amount of 3 to 50% by weight based on the total amount of the polymer compound.

5. The dispersion composition according to claim 1, wherein the polymer compound has an acid value in the range of 30 to 400 mg OH / g.

6. The dispersion composition according to claim 1, wherein the polymer compound has a weight average molecular weight in the range of 3,000 to 50,000.

7. An ink for an ink jet printer, comprising the dispersion composition according to claim 1. .